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WO2010074686A1 - Système et procédé d'hydroxyde électrochimique à faible énergie - Google Patents

Système et procédé d'hydroxyde électrochimique à faible énergie Download PDF

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Publication number
WO2010074686A1
WO2010074686A1 PCT/US2008/088242 US2008088242W WO2010074686A1 WO 2010074686 A1 WO2010074686 A1 WO 2010074686A1 US 2008088242 W US2008088242 W US 2008088242W WO 2010074686 A1 WO2010074686 A1 WO 2010074686A1
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WO
WIPO (PCT)
Prior art keywords
electrolyte
anode
cathode
exchange membrane
volt
Prior art date
Application number
PCT/US2008/088242
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English (en)
Inventor
Donald W. Kirk
J. Douglas Way
Allen J. Bard
Ryan J. Gilliam
Kasra Farsad
Valentin Decker
Original Assignee
Calera Corporation
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Filing date
Publication date
Application filed by Calera Corporation filed Critical Calera Corporation
Priority to US12/375,632 priority Critical patent/US7790012B2/en
Priority to CN200880118401XA priority patent/CN101878327A/zh
Priority to CA2666147A priority patent/CA2666147C/fr
Priority to BRPI0823394-2A priority patent/BRPI0823394A2/pt
Priority to GB0901413A priority patent/GB2467019B/en
Priority to PCT/US2008/088242 priority patent/WO2010074686A1/fr
Priority to EP08873036A priority patent/EP2291550A4/fr
Priority to US12/344,019 priority patent/US7887694B2/en
Priority to CA002652803A priority patent/CA2652803A1/fr
Priority to AU2008278301A priority patent/AU2008278301B2/en
Priority to CN200880023216.2A priority patent/CN101687648B/zh
Priority to EP08867440A priority patent/EP2118004A4/fr
Priority to EA201000896A priority patent/EA201000896A1/ru
Priority to JP2010540897A priority patent/JP2012513944A/ja
Priority to MX2010007197A priority patent/MX2010007197A/es
Priority to GB0901414A priority patent/GB2460910B8/en
Priority to BRPI0821515A priority patent/BRPI0821515A2/pt
Priority to KR1020107016361A priority patent/KR20100105860A/ko
Priority to PCT/US2008/088318 priority patent/WO2009086460A1/fr
Priority to TW097150781A priority patent/TW200946210A/zh
Priority to ARP080105752A priority patent/AR070056A1/es
Priority to US12/475,378 priority patent/US7753618B2/en
Priority to KR1020107027766A priority patent/KR20110033822A/ko
Priority to EP09716193A priority patent/EP2240257A1/fr
Priority to JP2011511869A priority patent/JP2011521879A/ja
Priority to MX2010012947A priority patent/MX2010012947A/es
Priority to GB0911440A priority patent/GB2461622B/en
Priority to PCT/US2009/045722 priority patent/WO2009146436A1/fr
Priority to CN200980101283.6A priority patent/CN101883736B/zh
Priority to CA2700715A priority patent/CA2700715A1/fr
Priority to BRPI0915192A priority patent/BRPI0915192A2/pt
Priority to EP09767687A priority patent/EP2207753A4/fr
Priority to US12/486,692 priority patent/US7754169B2/en
Priority to JP2011514787A priority patent/JP2011524253A/ja
Priority to AU2009260036A priority patent/AU2009260036B2/en
Priority to PCT/US2009/047711 priority patent/WO2009155378A1/fr
Priority to PCT/US2009/048511 priority patent/WO2010008896A1/fr
Priority to JP2011518768A priority patent/JP2011528405A/ja
Priority to EP09798527.9A priority patent/EP2212033A4/fr
Priority to AU2009271304A priority patent/AU2009271304B2/en
Priority to CA2700721A priority patent/CA2700721C/fr
Priority to US12/521,256 priority patent/US7875163B2/en
Priority to CN201410836715.0A priority patent/CN104722466A/zh
Priority to CN200980101611.2A priority patent/CN101984749B/zh
Priority to AU2009268397A priority patent/AU2009268397A1/en
Priority to BRPI0915447A priority patent/BRPI0915447A2/pt
Priority to US12/501,217 priority patent/US7749476B2/en
Priority to JP2011517648A priority patent/JP2011527664A/ja
Priority to KR1020117003141A priority patent/KR20110061546A/ko
Priority to CA2700765A priority patent/CA2700765A1/fr
Priority to CN2009801012200A priority patent/CN101878060A/zh
Priority to PCT/US2009/050223 priority patent/WO2010006242A1/fr
Priority to EP09795228A priority patent/EP2200732A4/fr
Priority to US12/503,557 priority patent/US8357270B2/en
Priority to KR1020117003467A priority patent/KR20110038691A/ko
Priority to EP09798723.4A priority patent/EP2245214B1/fr
Priority to CN2009801015529A priority patent/CN101910469A/zh
Priority to PCT/US2009/050756 priority patent/WO2010009273A1/fr
Priority to JP2011518896A priority patent/JP5373079B2/ja
Priority to AU2009270879A priority patent/AU2009270879B2/en
Priority to CA2700768A priority patent/CA2700768C/fr
Priority to US12/541,055 priority patent/US7993500B2/en
Priority to TW098144398A priority patent/TW201038773A/zh
Priority to ARP090105110A priority patent/AR075113A1/es
Priority to AU2010200225A priority patent/AU2010200225A1/en
Priority to US12/698,741 priority patent/US20100135882A1/en
Priority to US12/698,483 priority patent/US20100135865A1/en
Priority to US12/698,802 priority patent/US20100132556A1/en
Priority to GBGB1004571.4A priority patent/GB201004571D0/en
Priority to US12/788,255 priority patent/US20100313794A1/en
Priority to US12/794,198 priority patent/US7914685B2/en
Priority to HK10105950.5A priority patent/HK1139376A1/xx
Priority to IL206580A priority patent/IL206580A0/en
Priority to ZA2010/04552A priority patent/ZA201004552B/en
Publication of WO2010074686A1 publication Critical patent/WO2010074686A1/fr
Priority to US12/942,558 priority patent/US8333944B2/en
Priority to IL209365A priority patent/IL209365A0/en
Priority to US13/181,124 priority patent/US20110308964A1/en
Priority to US13/462,569 priority patent/US20120213688A1/en
Priority to US13/540,992 priority patent/US8894830B2/en
Priority to US13/887,986 priority patent/US9260314B2/en
Priority to JP2013192595A priority patent/JP5647314B2/ja
Priority to US14/534,559 priority patent/US20150083607A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/14—Alkali metal compounds
    • C25B1/16—Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
    • B01D53/326—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00 in electrochemical cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/402—Alkaline earth metal or magnesium compounds of magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • OH " hydroxide ions
  • One way to obtain OH ' in a solution is to dissolve an alkali hydroxide such as sodium hydroxide or magnesium hydroxide in the solution.
  • alkali hydroxide such as sodium hydroxide or magnesium hydroxide
  • conventional processes for producing hydroxides are very energy intensive, e g , the chlor-alkali process, and they emit significant amounts of carbon dioxide and other greenhouse gases into the environment.
  • the present invention pertains to a low energy electrochemical system and method of producing OH " utilizing an ion exchange membrane in an electrochemical cell
  • the system in one embodiment comprises an anionic or cationic exchange membrane positioned between a first electrolyte and a second electrolyte, the first electrolyte contacting an anode and the second electrolyte contacting a cathode
  • Suitable electrolytes comprise a saltwater including sodium chloride, seawater, brackish water or freshwater,
  • OH " forms at the cathode and protons form at the anode without a gas, e.g., chlorine or oxygen, forming at the anode.
  • a hydroxide solution e g, sodium hydroxide
  • an acid e.g., hydrochloric acid
  • OH forms when a volt of less than 0.1 V is applied across the electrodes.
  • the system comprises an electrochemical cell in which an anion exchange membrane separates a first electrolyte from a third electrolyte; a cation exchange membrane separates the third electrolyte from a first electrolyte; an anode is in contact with the first electrolyte; and a cathode is in contact with the second electrolyte.
  • OH forms at the cathode without a gas, e.g., chlorine or oxygen forming at the anode.
  • a hydroxide solution e.g., sodium hydroxide
  • an acid e.g., hydrochloric acid
  • OH forms when a volt of less than 0.1 V is applied across the electrodes.
  • the method comprises migrating ions across an ion exchange membrane that is situated between a first electrolyte and a second electrolyte, the first electrolyte contacting an anode and the second electrolyte contacting a cathode, by applying a voltage across the anode and cathode to form hydroxide ions at the cathode without forming a gas, e.g., chlorine or oxygen at the anode.
  • a gas e.g., chlorine or oxygen at the anode.
  • a hydroxide solution e.g., sodium hydroxide forms in the second electrolyte in contact with the cathode and an acid, e.g., hydrochloric acid forms in the first electrolyte in contact with the anode.
  • an acid e.g., hydrochloric acid
  • OH forms when a volt of less than 0.1 V is applied across the electrodes.
  • the method comprises applying a voltage across an anode and cathode, wherein (i) the anode is in contact with a first electrolyte that is also in contact with an anion exchange membrane; (ii) the cathode is in contact with a second electrolyte that is also in contact with a cation exchange membrane; and (iii) a third electrolyte is situated between the anion exchange membrane and the cation exchange membrane to form hydroxide ions at the cathode without forming a gas e.g., chlorine or oxygen at the anode.
  • a gas e.g., chlorine or oxygen
  • OH " forms at the cathode in contact the second electrolyte without a gas e.g., chlorine or oxygen at the anode.
  • a hydroxide solution e.g. sodium hydroxide
  • an acid e.g., hydrochloric acid
  • OH " forms when a volt of less than 0.1 V is applied across the electrodes.
  • the system and method are adapted for batch, semi-batch or continuous flows.
  • the system is adaptable to form OH " in solution, e.g., sodium hydroxide at the cathode, or an acidic solution, e.g., hydrochloric acid at the anode without forming a gas e.g., chlorine or oxygen at the anode.
  • the solution comprising OH " can be used to sequester CO2 by contacting the solution with CO2 and precipitating alkaline earth metal carbonates, e.g., calcium and magnesium carbonates and bicarbonates from a solution comprising alkaline earth metal ions as described United States Provisional Patent Application Serial No.
  • the precipitated carbonates in various embodiments, are useable as building products, e.g., cements, as described in United States Patent Applications herein incorporated by reference. Similarly, the system and method are adaptable for desalinating water as described in United States Patent Applications herein incorporated by reference.
  • Fig. 1 is an illustration of an embodiment of the present system.
  • Fig. 2 is an illustration of an embodiment of the present system.
  • Fig. 3 is an illustration of an embodiment of the present system.
  • Fig. 4 is an illustration of an embodiment of the present system.
  • Fig. 5 is an illustration of an embodiment of the present system.
  • Fig. 6 is an illustration of an embodiment of the present system.
  • Fig. 7 is a flow chart of an embodiment of the present method.
  • Fig. 8 is a flow chart of an embodiment of the present method.
  • hydroxide may not be produced, e.g., in embodiments where the pH of the electrolyte solution in contact with the cathode, as described herein, is kept constant or even decreases, there is no net production of hydroxide ions and can even be a decrease in hydroxide ion production. This can occur, e.g., in embodiments in which CO2 is introduced into the second electrolyte solution, as described further herein.
  • the present invention in various embodiments is directed to a low voltage electrochemical system and method for forming OH + in a solution, e.g., a saltwater solution, utilizing ion exchange membranes.
  • a solution e.g., a saltwater solution
  • ion exchange membranes On applying a voltage across a cathode and an anode, OH + forms in solution in the electrolyte contacted with the cathode, protons form in the solution contacted with the anode, and a gas e.g., chlorine or oxygen is not formed at the anode.
  • Hydroxide ions are formed where the voltage applied across the anode and cathode is less than 2.8, 2.7, 2.5, 2.4, 2.3, 2.2, 2.1 , 2.0, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1 , 1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 V.
  • hydroxide ions are formed where the voltage applied across the anode and cathode is less than 2.5 V without the formation of gas at the anode. In certain embodiments hydroxide ions are formed where the voltage applied across the anode and cathode is less than 2.2V. In certain embodiments hydroxide ions are formed where the voltage applied across the anode and cathode is less than 2.0V. In certain embodiments hydroxide ions are formed where the voltage applied across the anode and cathode is less thani .5 V. In certain embodiments hydroxide ions are formed where the voltage applied across the anode and cathode is less than 1.0V.
  • hydroxide ions are formed where the voltage applied across the anode and cathode is less than 0.8 V. In certain embodiments hydroxide ions are formed where the voltage applied across the anode and cathode is less than 0.7V. In certain embodiments hydroxide ions are formed where the voltage applied across the anode and cathode is less than 0.6V. In certain embodiments hydroxide ions are formed where the voltage applied across the anode and cathode is less than 0.5V. In certain embodiments hydroxide ions are formed where the voltage applied across the anode and cathode is less than 0.4V. In certain embodiments hydroxide ions are formed where the voltage applied across the anode and cathode is less than 0.3V.
  • hydroxide ions are formed where the voltage applied across the anode and cathode is less than 0.2V. In certain embodiments hydroxide ions are formed where the voltage applied across the anode and cathode is less than 0.1V. . In certain embodiments hydroxide ions are formed where the voltage applied across the anode and cathode is less than 0.05V. In various embodiments an acidic solution, e.g., hydrochloric acid is formed in the electrolyte in contact with the anode.
  • the present system is adaptable for batch and continuous processes as described herein.
  • the system comprises an electrochemical system including an ion exchange membrane (102, 124) separating a first electrolyte (104) from a second electrolyte (106), the first electrolyte contacting an anode (108) and the second electrolyte contacting a cathode (110).
  • ion exchange membrane includes membranes that are selectively permeable to one ion, or one type of ion (e.g., anions, or monovalent anions, or cations, or monovalent cations). In the system as illustrated in Fig.
  • first electrolyte (104) comprises an aqueous salt solution such as a saltwater, e.g., seawater, freshwater, brine, brackish water or the like.
  • second electrolyte (106) comprises a concentrated solution of sodium chloride; in other embodiments, second electrolyte may comprise saltwater.
  • first electrolyte (104) comprises a concentrated solution of sodium chloride
  • second electrolyte (106) comprises an aqueous solution such as a saltwater, e.g., seawater, freshwater, brine, brackish water or the like.
  • first electrolyte may comprise a saltwater.
  • anion exchange membrane (102) and/or cation exchange membrane (124) are any ion exchange membranes suitable for use in an acidic and/or basic electrolytic solution temperatures in the range from about 0 0 C to about 100 0 C, such as conventional ion exchange membranes well-known in the art, or any suitable ion exchange membrane.
  • Suitable anion exchange membranes are available from PCA GmbH of Germany, e.g., an anion exchange membrane identified as PCSA-250-250 can be used; similarly, a cation exchange membrane identified as PCSK 250-250 available from PCA GmbH can be used.
  • the ion exchange membranes are positioned to prevent mixing of the first and second electrolytes.
  • the electrochemical system (100, 200) includes first electrolyte inlet port (114) for inputting first electrolyte (104) into the system and second electrolyte inlet port (116) for inputting second electrolyte (106) into the system.
  • the cell includes outlet port (118) for draining first electrolyte from the system, and outlet port (120) for draining second electrolyte from the system.
  • the inlet and outlet ports are adaptable for various flow protocols including batch flow, semi-batch flow, or continuous flow.
  • the system includes a conduit, e.g., a duct (122) for directing hydrogen gas to the anode; in various embodiments the gas comprises hydrogen formed at the cathode (110); other sources of hydrogen gas can be used.
  • the first electrolyte (104) contacts the anode (108) and ion exchange membrane (102, 124) on a first side; and the second electrolyte contacts the cathode (106) and the ion exchange membrane at an opposed side to complete an electrical circuit that includes conventional voltage/current regulator (112).
  • the current/voltage regulator is adaptable to increase or decrease the current or voltage across the cathode and anode as desired.
  • second electrolyte (106) comprises sodium chloride
  • chloride ions migrate into the first electrolyte (104) from the second electrolyte (106) through the anion exchange membrane (102), and protons form in the electrolyte in contact with the anode (108).
  • second electrolyte (106) as hydroxide ions form in the electrolyte in contact with the cathode (110) and enter into the second electrolyte (106), and as chloride ions migrate from the second electrolyte into the first electrolyte (104), an aqueous solution of sodium hydroxide will form in second electrolyte (106).
  • the pH of the second electrolyte is adjusted, e.g., increases, decreases or does not change.
  • the pH of the first electrolyte will adjust depending on rate of introduction and/or removal of first electrolyte from the system. Also, as chloride ions migrate to the first electrolyte from the second electrolyte across the anion exchange membrane, hydrochloric acid will form in the first electrolyte. [0032] With reference to Fig.
  • first electrolyte (104) comprises sodium chloride
  • sodium ions migrate from the first electrolyte (104) to the second electrolyte (106) through the cation exchange membrane (124).
  • second electrolyte (106) as hydroxide ions form in the electrolyte in contact with the cathode (110) and enter into solution and with the migration of sodium ions into the second electrolyte, an aqueous solution of sodium hydroxide will form in second electrolyte (106).
  • the pH of the second electrolyte is adjusted, e.g., increases, decreases or does not change.
  • the pH of the first electrolyte will adjust depending on rate of introduction and/or removal of first electrolyte from the system, i.e., the pH of the first electrolyte may increase, decrease or does not change. Also, as sodium ions migrate from the first electrolyte across the cation exchange membrane to the second electrolyte, hydrochloric acid will form in the first electrolyte due to the presence of protons and chloride ions in the first electrolyte. [0034] With reference to Figs. 1 and 2, depending the flow of electrolytes in the system and the electrolytes used, e.g.
  • saltwater when a voltage is applied across the anode (108) and cathode (110) OH " will form in the in the second electrolyte (106), and consequently cause the pH of the second electrolyte to be adjusted. In one embodiment, when a voltage of about 0.1 V or less, 0.2 V or less.
  • NaOH was produced in the second electrolyte (106), and HCI in the first electrolyte (104) at a low operating voltage across the electrodes; it will be appreciated by those of ordinary skill in the art that the voltages may be adjusted up or down from these exemplary voltages; the minimum theoretical voltage is 0 or very close to 0, but to achieve a useful rate of production of hydroxide, a practical lower limit may be in some embodiments 0.001V or 0.01V, or 0.1 V, depending on the desired time for hydroxide production and/or pH adjustment, volume of second electrolyte solution, and other factors apparent to those of ordinary skill; i.e., in some embodiments the systems and methods are capable of producing hydroxide at voltages as low as 0.001V, or 0.01 V, or 0.1V, and can also produce hydroxide at higher voltages if more rapid production is desired, e.g., at 0.2-2. OV; in some embodiments the hydroxide is produced with no gas formation at the anode, e.
  • the system used included two 250 ml_ compartments separated by an anion exchange membrane in one embodiment, and a cation membrane in another embodiment.
  • a 0.5M NaCI 18M ⁇ aqueous solutions 28 g/L of NaCI was solvated with de-ionized water
  • Both the anode and cathode comprised a 10cm by 5cm 45 mesh Pt gauze.
  • H 2 gas was sparged under the Pt electrode, and the two electrodes were held at a voltage bias as indicated in Table 1 e.g., 0.4, 0.6 V and 1.0 V, for 30 minutes.
  • the pH of the electrolyte in contact with the anode before applying the voltage was 6.624.
  • the cathode compartment where the hydroxide formation occurred was stirred at 600 rpm. As set forth in Table 1 , significant changes in the pH in the cathode and anode compartment were achieved.
  • a pH difference of more than 0.5, 1 , 1 ,5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, or 12.0 pH units may be produced in a first electrolyte solution and a second electrolyte solution where the first electrolyte solution contacts an anode and the second electrolyte solution contacts a cathode, and the two electrolyte solutions are separated, e.g., by one or more ion exchange membrane, when a voltage of 1.0V or less, or 0.9V or less, or 0.8V or less, or 0.7 or less, or 0.6V or less, or 0.5V or less, or 0.4V or less, or 0.3V or less, or 0.2V or less, or 0.1V or less, or 0.05V or less, is applied across the anode and cathode.
  • the invention provides a system that is capable of producing a pH difference of more than 0.5 pH units between a first electrolyte solution and a second electrolyte solution where the first electrolyte solution contacts an anode and the second electrolyte solution contacts a cathode, and the two electrolyte solutions are separated, e.g., by one or more ion exchange membranes, when a voltage of 0.05V or less is applied across the anode and cathode.
  • the invention provides a system that is capable of producing a pH difference of more than 1.0 pH units between a first electrolyte solution and a second electrolyte solution where the first electrolyte solution contacts an anode and the second electrolyte solution contacts a cathode, and the two electrolyte solutions are separated, e.g., by one or more ion exchange membranes, when a voltage of 0.1V or less is applied across the anode and cathode.
  • the invention provides a system that is capable of producing a pH difference of more than 2.0 pH units between a first electrolyte solution and a second electrolyte solution where the first electrolyte solution contacts an anode and the second electrolyte solution contacts a cathode, and the two electrolyte solutions are separated, e.g., by one or more ion exchange membranes, when a voltage of 0.2V or less is applied across the anode and cathode.
  • the invention provides a system that is capable of producing a pH difference of more than 4.0 pH units between a first electrolyte solution and a second electrolyte solution where the first electrolyte solution contacts an anode and the second electrolyte solution contacts a cathode, and the two electrolyte solutions are separated, e.g., by one or more ion exchange membranes, when a voltage of 0.4V or less is applied across the anode and cathode.
  • the invention provides a system that is capable of producing a pH difference of more than 6 pH units between a first electrolyte solution and a second electrolyte solution where the first electrolyte solution contacts an anode and the second electrolyte solution contacts a cathode, and the two electrolyte solutions are separated, e.g., by one or more ion exchange membranes, when a voltage of 0.6V or less is applied across the anode and cathode.
  • the invention provides a system that is capable of producing a pH difference of more than 8 pH units between a first electrolyte solution and a second electrolyte solution where the first electrolyte solution contacts an anode and the second electrolyte solution contacts a cathode, and the two electrolyte solutions are separated, e.g., by one or more exchange membranes, when a voltage of 0.8V or less is applied across the anode and cathode
  • the invention provides a system that is capable of producing a pH difference of more than 8 pH units between a first electrolyte solution and a second electrolyte solution where the first electrolyte solution contacts an anode and the second electrolyte solution contacts a cathode, and the two electrolyte solutions are separated, e.g., by one or more ion exchange membranes, when a voltage of 1.0 V or less is applied across the anode and cathode.
  • the invention provides a system that is capable of producing a pH difference of more than 10 pH units between a first electrolyte solution and a second electrolyte solution where the first electrolyte solution contacts an anode and the second electrolyte solution contacts a cathode, and the two electrolyte solutions are separated, e.g., by one or more ion exchange membranes, when a voltage of 1.2V or less is applied across the anode and cathode.
  • the voltage need not be kept constant and that the voltage applied across the anode and the cathode may be very low, e.g., 0.05V or less, when the two electrolytes are the same pH or close in pH, and that the voltage may be increased as needed as the pH difference increases. In this way, the desired pH difference or production of hydroxide ions may be achieved with the minimum average voltage.
  • the average voltage may be less than 80%, 70%, 60%, or less than 50% of the voltages given in the previous paragraph for particular embodiments.
  • hydrogen gas formed at the cathode (110) is directed to the anode (108). Without being bound to any theory, it is believed that the gas is adsorbed and/or absorbed into the anode and subsequently forms protons at the anode.
  • one or more of the electrolyte solutions is depleted in divalent cations, e.g., in magnesium or calcium, during parts of the process where the electrolyte is in contact with the ion exchange membrane (or membranes, see embodiments described below in which more than one membrane is used). This is done to prevent scaling of the membrane, if necessary for that particular membrane.
  • divalent cations e.g., in magnesium or calcium
  • the total concentration of divalent cations in the electrolyte solutions when they are in contact with the ion exchange membrane or membranes for any appreciable time is less than 0.06 mol/kg solution, or less than 0.06 mol/kg solution, or less than 0.04 mol/kg solution, or less than 0.02 mol/kg solution, or less than 0.01 mol/kg solution, or less than 0.005 mol/kg solution, or less than 0.001 mol/kg solution, or less than 0.0005 mol/kg solution, or less than 0.0001 mol/kg solution, or less than 0.00005 mol/kg solution.
  • the present system (300) includes an electrolytic cell comprising an anode (108) contacting a first electrolyte (104); an anion exchange membrane (102) separating the first electrolyte from a third electrolyte (130); a second electrolyte contacting a cathode (110), and a cation exchange membrane (124) separating the second electrolyte from the third electrolyte.
  • the ion exchange membranes are positioned in the system to prevent mixing of the first and second electrolytes.
  • a current/voltage regulator (112) is adaptable to increase or decrease the current or voltage across the cathode and anode in the system as desired.
  • the system of Fig. 3 is adaptable for batch, semi-batch and continuous operation.
  • the first electrolyte (104), second electrolyte (106) and third electrolyte (130) in various embodiments comprise e.g., saltwater including seawater, freshwater, brine, or brackish water or the like.
  • the third electrolyte (130) comprise substantially a solution of a sodium chloride.
  • anion exchange membrane (102) and cation exchange membrane (124) of Fig. 3 are any suitable ion exchange membranes suitable for use in an acidic and/or basic solution at operating temperatures in an aqueous solution in the range from about 0 0 C to about 100 0 C, or higher depending on the pressure in the system such as conventional ion exchange membranes well- known in the art, or any suitable ion exchange membrane.
  • Suitable anion exchange membranes are available from PCA GmbH of Germany, e.g., an anion membrane identified as PCSA-250-250 can be used; similarly, a cation membrane identified as PCSK 250-250 available from PCA GmbH can be used.
  • the electrochemical cell includes first electrolyte inlet port (114) adaptable for inputting first electrolyte (104) into the system; second electrolyte inlet port (116) for inputting second electrolyte (106) into the system; and third inlet port (126) for inputting third electrolyte into the system. Additionally, the cell includes first outlet port (118) for draining first electrolyte; second outlet port (120) for draining second electrolyte; and third outlet port (128) for draining third electrolyte. As will be appreciated by one ordinarily skilled, the inlet and outlet ports are adaptable for various flow protocols including batch flow, semi-batch flow, or continuous flow.
  • the system includes a conduit, e.g., a duct (122) for directing gas to the anode; in various embodiments the gas comprises hydrogen formed at the cathode (110).
  • a conduit e.g., a duct (122) for directing gas to the anode; in various embodiments the gas comprises hydrogen formed at the cathode (110).
  • third electrolyte (130) comprises sodium chloride
  • chloride ions migrate into the first electrolyte (104) from the third electrolyte (130) through the anion exchange membrane (102); sodium ions migrate to the second electrolyte (106) from the third electrolyte (130); protons form at the anode (104); and hydrogen gas forms at the cathode (110).
  • the pH of the second electrolyte solution is increased; in another embodiment, when a voltage of 0.01 to 2.5 V, or 0.01V to 2.0V, or 0.1 V to 2.0V, or 0.1V to 1.5V, or 0.1 V to 1.0V, or 0.1 V to 0.8V, or 0.1 V to 0.6V, or 0.1 V to 0.4V, or 0.1V to 0.2V, or 0.01V to 1.5V, or 0.01 V to 1.0V, or 0.01 V to 1.0V, or 0.01 V to 0.8V, or 0.1 V to 0.6V, or 0.1 V to 0.4V, or 0.1V to 0.2V, or 0.01V to 1.5V, or 0.01 V to 1.0V, or 0.01V to 1.0V, or 0.01V to 0.01V to 0.01V to
  • a volt of about 0.6 volt or less is applied across the anode and cathode; in another embodiment, a volt of about 0.1 to 0.6 volt or less is applied across the anode and cathode; in yet another embodiment, a voltage of about 0.1 to 1 volt or less is applied across the anode and cathode.
  • first electrolyte (104) as proton form in the electrolyte in contact with the anode (108) and enter into the solution concurrent with migration of chloride ions from the third electrolyte (130) to the first electrolyte (104), increasingly an acidic solution will form in first electrolyte (104).
  • the pH of the solution will be adjusted as noted above.
  • hydrogen gas formed at the cathode (110) is directed to the anode (108).
  • hydrogen gas is adsorbed and/or absorbed into the anode and subsequently forms protons at the anode in contact with the first electrolyte (104).
  • a gas such as oxygen or chlorine does not form at the anode (108). Accordingly, as can be appreciated, with the formation of protons at the anode and migration of chlorine into the first electrolyte, hydrochloric acid is obtained in the first electrolyte (104).
  • a cation exchange membrane is in contact with the anode (108) on one surface, and in contact with the first electrolyte (104) at an opposed surface.
  • H + formed at or near the anode will migrate into the first electrolyte through the cation exchange membrane to cause the pH of the first electrolyte to be adjusted as discussed with reference to the system of Fig. 3.
  • an anion exchange membrane is in contact with the cathode (110) on one surface, and in contact with the second electrolyte (106) at an opposed surface.
  • OH " formed at or near the anode will migrate into the first electrolyte to cause the pH of the second electrolyte to be adjusted as discussed with reference to the system of Fig. 3.
  • the hydrogen gas formed at the cathode (110) can be redirected to the anode (108) without contacting the second (106) or first (104) electrolyte.
  • Fig. 5 illustrates a variation of the invention where at least two of the systems of Fig. 4 are configured to operate together.
  • hydroxide ions form at the cathode (110) and enter into second electrolyte (106) and with the migration of sodium ions into the second electrolyte from the third electrolyte (130), an aqueous solution of sodium hydroxide will from in second electrolyte (106).
  • the pH of the second electrolyte is adjusted, e.g., increases, decreases or does not change. Also with reference to Fig.
  • first electrolyte (104) as proton form at the anode (108) and enter into the solution concurrent with migration of chloride ions from the third electrolyte (130) to the first electrolyte (104), increasingly an acidic solution will form in first electrolyte (104).
  • Fig. 6 illustrates a variation of the system of Fig. 3 arranged for continuous or semi-continuous flow.
  • hydroxide ions form at the cathode (110)
  • protons form at the anode and gas, e.g., chlorine or oxygen does not form at the anode (108).
  • third electrolyte (130) comprises sodium chloride
  • chloride ions migrate into the first electrolyte (104) from the third electrolyte (130) through the anion exchange membrane (102); sodium ions migrate to the second electrolyte (106) from the third electrolyte (130) through the cation exchange membrane (124); protons form at the anode (104); and hydrogen gas forms at the cathode (110).
  • first electrolyte (104) as proton form at the anode (108) and enter into the solution concurrent with migration of chloride ions from the third electrolyte (130) to the first electrolyte (104), increasingly an acidic solution will form in first electrolyte (104).
  • the pH of the solution will be adjusted.
  • the present method in one embodiment (700) comprises a step (702) of migrating ions across an ion exchange membrane (102) that is situated between a first electrolyte (104) and a second electrolyte (106), the first electrolyte contacting an anode (108) and the second electrolyte contacting a cathode (110), by applying a voltage across the anode and cathode to form hydroxide ions at the cathode without forming a gas at the anode.
  • a voltage across the anode and cathode to form hydroxide ions at the cathode without forming a gas at the anode.
  • the present method (800) comprises a step (802) of applying a voltage across an anode (108) and cathode (110), wherein: (i) the anode is in contact with a first electrolyte (104) that is also in contact with an anion exchange membrane (102); (ii) the cathode is in contact with a second electrolyte (106) that is also in contact with a cation exchange membrane; and
  • a third electrolyte (130) is situated between the anion exchange membrane and the cation exchange membrane to form hydroxide ions at the cathode without forming a gas at the anode.
  • hydroxide ions from the cathode (110) and enter in to the second electrolyte (106) concurrent with migration of sodium ions into the second electrolyte from the third electrolyte, an aqueous solution of sodium hydroxide will form in second electrolyte (106). Consequently, depending on the voltage applied across the system and the flow rate of the second electrolyte (106) through the system, the pH of the second electrolyte is adjusted.
  • CO2 is dissolved into the second electrolyte solution; as protons are removed from the second electrolyte solution more CO2 may be dissolved in the form of bicarbonate and/or carbonate ions; depending on the pH of the second electrolyte the balance is shifted toward bicarbonate or toward carbonate, as is well understood in the art.
  • the pH of the second electrolyte solution may decrease, remain the same, or increase, depending on the rate of removal of protons compared to rate of introduction of CO2.
  • hydroxide need form in these embodiments, or that hydroxide may not form during one period but form during another period.
  • another electrochemical system as described herein may be used to produce concentrated hydroxide, which, when added to the second electrolyte containing the dissolved CO2, causes the formation of a precipitate of carbonate and/or bicarbonate compounds such as calcium carbonate or magnesium carbonate and/or their bicarbonates.
  • divalent cations such as magnesium and/or calcium are present in certain solutions used in the process, and/or are added.
  • the precipitated carbonate compound can be used as cements and building material as described in United States Patent Applications incorporated herein by reference.
  • the acidified first electrolyte solution 104 is utilized to dissolve a calcium and/or magnesium rich mineral, such as mafic mineral including serpentine or olivine, for precipitating carbonates and bicarbonates as described above.
  • a calcium and/or magnesium rich mineral such as mafic mineral including serpentine or olivine
  • the acidified stream can be employed to dissolve calcium and/or magnesium rich minerals such as serpentine and olivine to create the electrolyte solution that can be charged with bicarbonate ions and then made sufficiently basic to precipitate carbonate compounds.
  • Such precipitation reactions and the use of the precipitates in cements are described in the United States Patent Applications incorporated by herein by reference.
  • the carbonate and bicarbonate solution is disposed of in a location where it will be stable for extended periods of time.
  • the carbonate/bicarbonate electrolyte solution can be pumped to an ocean depth where the temperature and pressure are sufficient to keep the solution stable over at least the time periods set forth above.

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Abstract

L'invention concerne un procédé et un système à faible énergie servant à former des ions hydroxyde dans une cellule électrochimique. En appliquant une basse tension à travers l'anode et la cathode, des ions hydroxyde se forment dans l'électrolyte contenant la cathode, des protons se forment à l'anode mais un gaz, par ex. le chlore ou l'oxygène ne se forme pas à l'anode.
PCT/US2008/088242 2007-06-28 2008-12-23 Système et procédé d'hydroxyde électrochimique à faible énergie WO2010074686A1 (fr)

Priority Applications (82)

Application Number Priority Date Filing Date Title
US12/375,632 US7790012B2 (en) 2008-12-23 2008-12-23 Low energy electrochemical hydroxide system and method
CN200880118401XA CN101878327A (zh) 2008-12-23 2008-12-23 低能电化学氢氧根系统和方法
CA2666147A CA2666147C (fr) 2008-12-23 2008-12-23 Methode et systeme electrochimiques peu energivores de production d'ions hydroxydes
BRPI0823394-2A BRPI0823394A2 (pt) 2008-12-23 2008-12-23 Sistema e método eletroquímico de hidróxido de baixa energia
GB0901413A GB2467019B (en) 2008-12-23 2008-12-23 Low-energy electrochemical hydroxide system and method
PCT/US2008/088242 WO2010074686A1 (fr) 2008-12-23 2008-12-23 Système et procédé d'hydroxyde électrochimique à faible énergie
EP08873036A EP2291550A4 (fr) 2008-12-23 2008-12-23 Système et procédé d'hydroxyde électrochimique à faible énergie
US12/344,019 US7887694B2 (en) 2007-12-28 2008-12-24 Methods of sequestering CO2
CA002652803A CA2652803A1 (fr) 2007-12-28 2008-12-24 Procedes de sequestration du co2
AU2008278301A AU2008278301B2 (en) 2007-12-28 2008-12-24 Methods of sequestering CO2
CN200880023216.2A CN101687648B (zh) 2007-12-28 2008-12-24 封存co2的方法
EP08867440A EP2118004A4 (fr) 2007-12-28 2008-12-24 Procédés de séquestration de co2
EA201000896A EA201000896A1 (ru) 2007-12-28 2008-12-24 Способы связывания co
JP2010540897A JP2012513944A (ja) 2007-12-28 2008-12-24 Ｃｏ２を捕捉する方法
MX2010007197A MX2010007197A (es) 2007-12-28 2008-12-24 Metodos de secuestro de dioxido de carbono.
GB0901414A GB2460910B8 (en) 2007-12-28 2008-12-24 Methods of sequestering CO2.
BRPI0821515A BRPI0821515A2 (pt) 2007-12-28 2008-12-24 métodos de captura de co2
KR1020107016361A KR20100105860A (ko) 2007-12-28 2008-12-24 Ｃｏ2 분리 방법
PCT/US2008/088318 WO2009086460A1 (fr) 2007-12-28 2008-12-24 Procédés de séquestration de co2
TW097150781A TW200946210A (en) 2007-12-28 2008-12-26 Methods of sequestering CO2
ARP080105752A AR070056A1 (es) 2007-12-28 2008-12-29 Metodos para retirar co2
US12/475,378 US7753618B2 (en) 2007-06-28 2009-05-29 Rocks and aggregate, and methods of making and using the same
KR1020107027766A KR20110033822A (ko) 2008-05-29 2009-05-29 암석 및 골재, 및 이의 제조 방법 및 용도
EP09716193A EP2240257A1 (fr) 2008-05-29 2009-05-29 Roches et agrégats ainsi que leurs procédés de production et d utilisation
JP2011511869A JP2011521879A (ja) 2008-05-29 2009-05-29 岩石および骨材、ならびにそれらを作製し使用する方法
MX2010012947A MX2010012947A (es) 2008-05-29 2009-05-29 Rocas y agregados y metodos para obtener y usar los mismos.
GB0911440A GB2461622B (en) 2008-05-29 2009-05-29 Rocks and aggregate, and methods of making and using the same
PCT/US2009/045722 WO2009146436A1 (fr) 2008-05-29 2009-05-29 Roches et agrégats ainsi que leurs procédés de production et d’utilisation
CN200980101283.6A CN101883736B (zh) 2008-06-17 2009-06-17 利用金属氧化物废料源的方法和系统
CA2700715A CA2700715A1 (fr) 2008-06-17 2009-06-17 Procedes et systemes d'utilisation de sources de dechets d'oxydes metalliques
BRPI0915192A BRPI0915192A2 (pt) 2008-06-17 2009-06-17 métodos e sistemas para utilização de fontes de resíduos de óxidos de metal
EP09767687A EP2207753A4 (fr) 2008-06-17 2009-06-17 Procédés et systèmes d'utilisation de sources de déchets d'oxydes métalliques
US12/486,692 US7754169B2 (en) 2007-12-28 2009-06-17 Methods and systems for utilizing waste sources of metal oxides
JP2011514787A JP2011524253A (ja) 2008-06-17 2009-06-17 金属酸化物の廃棄物源を利用するための方法およびシステム
AU2009260036A AU2009260036B2 (en) 2008-06-17 2009-06-17 Methods and systems for utilizing waste sources of metal oxides
PCT/US2009/047711 WO2009155378A1 (fr) 2008-06-17 2009-06-17 Procédés et systèmes d'utilisation de sources de déchets d'oxydes métalliques
PCT/US2009/048511 WO2010008896A1 (fr) 2008-07-16 2009-06-24 Système électrochimique à 4 cellules basse énergie comportant du dioxyde de carbone gazeux
JP2011518768A JP2011528405A (ja) 2008-07-16 2009-06-24 二酸化炭素ガスを使用する低エネルギー４セル電気化学システム
EP09798527.9A EP2212033A4 (fr) 2008-07-16 2009-06-24 Système électrochimique à 4 cellules basse énergie comportant du dioxyde de carbone gazeux
AU2009271304A AU2009271304B2 (en) 2008-07-16 2009-06-24 Low-energy 4-cell electrochemical system with carbon dioxide gas
CA2700721A CA2700721C (fr) 2008-07-16 2009-06-24 Systeme electrochimique a 4 cellules basse energie comportant du dioxyde de carbone gazeux
US12/521,256 US7875163B2 (en) 2008-07-16 2009-06-24 Low energy 4-cell electrochemical system with carbon dioxide gas
CN201410836715.0A CN104722466A (zh) 2008-07-16 2009-06-24 使用二氧化碳气体的低能量4-电池电化学系统
CN200980101611.2A CN101984749B (zh) 2008-07-16 2009-06-24 使用二氧化碳气体的低能量4-电池电化学系统
AU2009268397A AU2009268397A1 (en) 2008-07-10 2009-07-10 Production of carbonate-containing compositions from material comprising metal silicates
BRPI0915447A BRPI0915447A2 (pt) 2008-07-10 2009-07-10 produção de composições contendo carbonato por meio de material compreendendo silicatos metálicos
US12/501,217 US7749476B2 (en) 2007-12-28 2009-07-10 Production of carbonate-containing compositions from material comprising metal silicates
JP2011517648A JP2011527664A (ja) 2008-07-10 2009-07-10 含金属シリケート材料からの炭酸塩含有組成物の製造
KR1020117003141A KR20110061546A (ko) 2008-07-10 2009-07-10 금속 실리케이트를 포함하는 물질로부터 탄산염 함유 조성물을 제조하는 방법
CA2700765A CA2700765A1 (fr) 2008-07-10 2009-07-10 Production de compositions contenant du carbonate a partir d'un materiau comportant des silicates metalliques
CN2009801012200A CN101878060A (zh) 2008-07-10 2009-07-10 从包含金属硅酸盐的材料中制备含碳酸盐的组合物
PCT/US2009/050223 WO2010006242A1 (fr) 2008-07-10 2009-07-10 Production de compositions contenant du carbonate à partir d'un matériau comportant des silicates métalliques
EP09795228A EP2200732A4 (fr) 2008-07-10 2009-07-10 Production de compositions contenant du carbonate à partir d'un matériau comportant des silicates métalliques
US12/503,557 US8357270B2 (en) 2008-07-16 2009-07-15 CO2 utilization in electrochemical systems
KR1020117003467A KR20110038691A (ko) 2008-07-16 2009-07-15 전기화학 시스템에서 ｃｏ２를 사용하는 방법
EP09798723.4A EP2245214B1 (fr) 2008-07-16 2009-07-15 Système et méthode électrochimique pour utilisation du co2
CN2009801015529A CN101910469A (zh) 2008-07-16 2009-07-15 电化学系统中的co2利用
PCT/US2009/050756 WO2010009273A1 (fr) 2008-07-16 2009-07-15 Utilisation du co<sb>2</sb> dans des systèmes électrochimiques
JP2011518896A JP5373079B2 (ja) 2008-07-16 2009-07-15 電気化学システム中でのｃｏ２の利用
AU2009270879A AU2009270879B2 (en) 2008-07-16 2009-07-15 CO2 utilization in electrochemical systems
CA2700768A CA2700768C (fr) 2008-07-16 2009-07-15 Utilisation du co<sb>2</sb> dans des systemes electrochimiques
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AU2010200225A AU2010200225A1 (en) 2007-12-28 2010-01-21 Methods of sequestering CO2
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US12/788,255 US20100313794A1 (en) 2007-12-28 2010-05-26 Production of carbonate-containing compositions from material comprising metal silicates
US12/794,198 US7914685B2 (en) 2007-06-28 2010-06-04 Rocks and aggregate, and methods of making and using the same
HK10105950.5A HK1139376A1 (en) 2007-12-28 2010-06-14 Methods of sequestering co2
IL206580A IL206580A0 (en) 2007-12-28 2010-06-23 Methods of sequestering co2
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US12/942,558 US8333944B2 (en) 2007-12-28 2010-11-09 Methods of sequestering CO2
IL209365A IL209365A0 (en) 2008-05-29 2010-11-16 Rocks and aggregate, and methods of making and using the same
US13/181,124 US20110308964A1 (en) 2008-12-23 2011-07-12 Gas diffusion anode and co2 cathode electrolyte system
US13/462,569 US20120213688A1 (en) 2007-12-28 2012-05-02 Methods of sequestering co2
US13/540,992 US8894830B2 (en) 2008-07-16 2012-07-03 CO2 utilization in electrochemical systems
US13/887,986 US9260314B2 (en) 2007-12-28 2013-05-06 Methods and systems for utilizing waste sources of metal oxides
JP2013192595A JP5647314B2 (ja) 2008-07-16 2013-09-18 電気化学システム中でのｃｏ２の利用
US14/534,559 US20150083607A1 (en) 2008-07-16 2014-11-06 Co2 utilization in electrochemical systems

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US12/163,205 Continuation-In-Part US7744761B2 (en) 2007-06-28 2008-06-27 Desalination methods and systems that include carbonate compound precipitation
PCT/US2008/088246 Continuation-In-Part WO2010074687A1 (fr) 2007-06-28 2008-12-23 Système et procédé de transfert de protons électrochimique à faible énergie
PCT/US2009/032301 Continuation-In-Part WO2010087823A1 (fr) 2008-07-16 2009-01-28 Solution d'ions bicarbonates électrochimique à basse énergie

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US12/344,019 Continuation-In-Part US7887694B2 (en) 2007-06-28 2008-12-24 Methods of sequestering CO2
PCT/US2009/032301 Continuation-In-Part WO2010087823A1 (fr) 2008-07-16 2009-01-28 Solution d'ions bicarbonates électrochimique à basse énergie
PCT/US2009/048511 Continuation-In-Part WO2010008896A1 (fr) 2008-07-16 2009-06-24 Système électrochimique à 4 cellules basse énergie comportant du dioxyde de carbone gazeux

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TW201038773A (en) 2010-11-01
CN101878327A (zh) 2010-11-03
EP2291550A1 (fr) 2011-03-09
CA2666147C (fr) 2011-05-24
GB2467019B (en) 2011-04-27
EP2291550A4 (fr) 2011-03-09
BRPI0823394A2 (pt) 2015-06-16
GB0901413D0 (en) 2009-03-11
CA2666147A1 (fr) 2010-02-02
US7790012B2 (en) 2010-09-07
AR075113A1 (es) 2011-03-09
US20100155258A1 (en) 2010-06-24

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